U.S. patent application number 10/485840 was filed with the patent office on 2004-09-02 for process for the preparation of diketopyrrolopyrroles.
Invention is credited to Morton, Colin, Ruffieux, Vincent, Smith, David Macdonald.
Application Number | 20040171847 10/485840 |
Document ID | / |
Family ID | 27224407 |
Filed Date | 2004-09-02 |
United States Patent
Application |
20040171847 |
Kind Code |
A1 |
Morton, Colin ; et
al. |
September 2, 2004 |
Process for the preparation of diketopyrrolopyrroles
Abstract
The present invention relates to a process for the preparation
of diketopyrrolopyrroles of the formula (I), wherein A1, A2, A3 and
A4 are as defined in the description of the present invention, to
new diketopyrrolopyrroles of the general formula I obtainable by
the process, and the use of the new diketopyrrolopyrroles of the
general formula I for the preparation of inks, colorants, pigmented
plastics for coatings, non-impact-printing material, color filters,
cosmetics, polymeric ink particles, toners, dye lasers and
electroluminescent devices, or as fluorescent markers for
immunoassays and fluorescent tracers for leak detection of fluids.
Furthermore the present invention relates to diketopyrrolopyrrole
analogues of the general formula (II), wherein A1, A2 and A3 are
defined in the description of the present invention, which are
intermediates in the process for the preparation of
diketopyrrolopyrroles of the formula I and can be used as crystal
growth regulators. 1
Inventors: |
Morton, Colin; (Basel,
CH) ; Smith, David Macdonald; (Fife, GB) ;
Ruffieux, Vincent; (Marly, CH) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
27224407 |
Appl. No.: |
10/485840 |
Filed: |
February 4, 2004 |
PCT Filed: |
September 3, 2002 |
PCT NO: |
PCT/EP02/09792 |
Current U.S.
Class: |
548/453 |
Current CPC
Class: |
C09B 57/004 20130101;
C09K 2211/1044 20130101; C07D 487/04 20130101; C09K 2211/1011
20130101; C09K 11/06 20130101; C07D 491/04 20130101; C09K 2211/1033
20130101; C09B 67/0039 20130101 |
Class at
Publication: |
548/453 |
International
Class: |
C07D 487/02 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 11, 2001 |
EP |
01810875.3 |
Dec 20, 2001 |
EP |
01811249.0 |
Mar 22, 2002 |
EP |
02405223.5 |
Claims
1. A process for the preparation of diketopyrrolopyrroles of the
general formula 47comprising reacting a compound of the formula
48with a primary amine of the formula A.sup.4-NH.sub.2 (III),
wherein A.sup.1 and A.sup.2 are C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl,
C.sub.5-C.sub.8cycloalkyl, C.sub.5-C.sub.8cycloalkenyl, aryl or
heteroaryl, A.sup.3 is hydrogen, C.sub.1-C.sub.18alkyl,
cyanomethyl, Ar.sup.3, --CR.sup.30R.sup.31R--(CH.s-
ub.2).sub.m--Ar.sup.3 or Y--R.sup.32, wherein R.sup.30 and R.sup.31
independently of each other stand for hydrogen or
C.sub.1-C.sub.4alkyl, or phenyl which can be substituted up to
three times with C.sub.1-C.sub.3alkyl, Ar.sup.3 stands for aryl,
C.sub.5-C.sub.8cycloalkyl- , C.sub.5-C.sub.8cycloalkenyl or
heteroaryl, which can be substituted one to three times with
C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxy, halogen or phenyl,
which can be substituted with C.sub.1-C.sub.8alkyl or
C.sub.1-C.sub.8alkoxy one to three times, and m stands for 0, 1, 2,
3 or 4, Y is --C(O)--, --C(O)O--, --C(O)NH--, --SO.sub.2NH-- or
--SO.sub.2-- and R.sup.32 is C.sub.1-C.sub.16alkyl, Ar.sup.3, or
aralkyl, and A.sup.4 is C.sub.1-C.sub.18alkyl or Ar.sup.3.
2. The process according to claim 1, wherein the compound of the
formula II, wherein A.sup.3 is different from a hydrogen atom, is
obtained by reacting a compound of the formula 49with a compound of
the formula A.sup.9-X (V), wherein A.sup.1, A.sup.2 and A.sup.3
have the meanings as given in claim 1 and X is a leaving group.
3. The process according to claim 1 or 2, wherein the compound of
the formula IV is obtained by heating a compound of the formula
50in an inert solvent, wherein A.sup.1 and A.sup.2 have the
meanings as given in claim 1 and R is C.sub.1-C.sub.18alkyl, in
particular C.sub.1-C.sub.4alkyl, aryl, in particular phenyl, or
aralkyl, in particular benzyl, which can be substituted one to
three times with C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxy, or
halogen.
4. A diketopyrrolopyrrole of the general formula 51wherein A.sup.1,
A.sup.2 and A.sup.3 have the meanings as given in claim 1 and
A.sup.4 is Ae.
5. The diketopyrrolopyrrole according to claim 4, wherein A.sup.1
and A.sup.2 are radicals of the formula 52R.sup.1 and R.sup.2 are
independently of each other hydrogen, halogen,
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18 alkoxy,
C.sub.1-C.sub.18alkylmercapto, C.sub.1-C.sub.18alkylamino,
C.sub.1-C.sub.16alkoxycarbonyl, C.sub.1-C.sub.18alkylaminocarbonyl,
--CN, --NO.sub.2, trifluoromethyl, C.sub.5-C.sub.8cycloalkyl,
--C.dbd.N--(C.sub.1-C.sub.18alkyl), phenyl, 53imidazolyl,
pyrrazolyl, triazolyl, piperazinyl, pyrrolyl, oxazolyl,
benzoxazolyl, benzothiazolyl, benzimidazolyl, morpholinyl,
piperidinyl or pyrrolidinyl, --CONX.sup.5X.sup.6, --C(O)OX.sup.7 or
--SO.sub.2X.sup.9; wherein X.sup.5 and X.sup.6 are hydrogen, linear
or branched C.sub.1-10-alkyl, C.sub.5-10-cycloalkyl or
C.sub.6-10-aryl, X.sup.7 is hydrogen, linear or branched
C.sub.1-10-alkyl, C.sub.5-10-cycloalkyl or C.sub.6-10-aryl, X.sup.9
is hydrogen, linear or branched C.sub.1-10-alkyl,
C.sup.5-10-cycloalkyl, C.sub.7-10-aralkyl, C.sub.6-10-aryl or
--NX.sup.10X.sup.11, wherein X.sup.10 and X.sup.11 are hydrogen,
linear or branched C.sub.1-10-alkyl, C.sub.7-10-aralkyl or
C.sub.6-10-aryl, G is --CH.sub.2--, --CH(CH.sub.3)--,
--C(CH.sub.3).sub.2--, --CH.dbd.N--, --N.dbd.N--, --O--, --S--,
--SO--, --SO.sub.2--, --SO.sub.2NH--, --CONH-- or --NR.sup.7--,
R.sup.3 and R.sup.4 are independently of each other hydrogen,
halogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.18alkoxy or --CN,
R.sup.5 and R.sup.6 are independently of each other hydrogen,
halogen or C.sub.1-C.sub.6alkyl, and R.sup.7 is hydrogen or
C.sub.1-C.sub.6alkyl; or radicals of the formula 5455wherein
R.sup.21, R.sup.22, R.sup.23, R.sup.25 and R.sup.26 are
independently of each other hydrogen, C.sub.1-C.sub.6alkyl, a
hydroxyl group, a mercapto group, C.sub.1-C.sub.8alkoxy,
C.sub.1-C.sub.8alkylthio, halogen, halo-C.sub.1-C.sub.8alkyl, a
cyano group, an aldehyde group, a ketone group, a carboxyl group,
an ester group, a carbamoyl group, an amino group, a nitro group, a
silyl group or a siloxanyl group and R.sup.24 is a
C.sub.1-C.sub.6alkyl group.
6. The diketopyrrolopyrrole according to claim 4 or 5, wherein
A.sup.1 and A.sup.2 are radicals of the formula 56wherein R.sup.1
and R.sup.2 are independently of each other hydrogen, chloro,
bromo, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.6alkoxy,
C.sub.1-C.sub.6alkylamino, phenyl or CN, G is --O--, --NR.sup.7--,
--N.dbd.N-- or --SO.sub.2--, R.sup.3 and R.sup.4 are hydrogen, and
R.sup.7 is hydrogen, methyl or ethyl.
7. The diketopyrrolopyrrole according to any of claims 4 to 6,
wherein A.sup.3 is cyanomethyl, C.sub.1-C.sub.8alkyl such as
methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl,
tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl,
n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and
2-ethylhexyl, Y--R.sup.32 wherein Y is --C(O)-- and R.sup.32 is
57wherein R.sup.40 is C.sub.1-C.sub.4alkyl,
--O--C.sub.1-C.sub.4alkyl, or --S--C.sub.1-C.sub.4alkyl, or
--(CH.sub.2).sub.m--Ar wherein m is 1 and Ar is a group of the
formula 58which can be substituted one to three times with
C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxy, halogen or phenyl.
8. The diketopyrrolopyrrole according to any of claims 4 to 7,
wherein A.sup.4 is 59which can be substituted one to three times
with C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxy, halogen or
phenyl.
9. A method of coloring a high molecular weight organic material by
incorporating therein a diketopyrrolopyrrole of formula I according
to any of claims 4 to 8.
10. A composition comprising (a) 0.01 to 50% by weight, based on
the total weight of the colored high molecular weight organic
material, of the diketopyrrolopyrrole of formula I according to any
of claims 4 to 8, and (b) 99.99 to 50% by weight, based on the
total weight of the colored high molecular weight organic material,
of a high molecular organic material, and (c) optionally, customary
additives in effective amounts.
11. A pyrrolinone of the general formula 60wherein A.sup.1, A.sup.2
and R have the meanings as given in claim 3.
12. Use of the diketopyrrolopyrroles of formula I according to any
of claims 4 to 8 for the preparation of inks, colorants, pigmented
plastics for coatings, non-impact-printing material, color filters,
cosmetics, polymeric ink particles, toners, dye lasers and
electroluminescent devices, or as fluorescent markers for
immunoassays and fluorescent tracers for leak detection of
fluids.
13. A diketopyrrolopyrrole analogue of formula II 61wherein
A.sup.1, A.sup.2 and A.sup.3 have the meanings as given in claim 1,
with the proviso that
3,5,6-triphenyl-1H-furo[3,4-c]pyrrole-1,4-(5H)-dione is
excluded.
14. Use of the diketopyrrolopyrrole analogues of formula II
according to claim 13 as crystal growth regulators.
Description
[0001] The present invention relates to a process for the
preparation of diketopyrrolopyrroles ("DPPs") of the formula 1, to
new diketopyrrolopyrroles of the general formula I obtainable by
the process, and the use of the new diketopyrrolopyrroles of the
general formula I for the preparation of inks, colorants, pigmented
plastics for coatings, non-impact-printing material, color filters,
cosmetics, polymeric ink particles, toners, dye lasers and
electroluminescent devices, or as fluorescent markers for
immunoassays and fluorescent tracers for leak detection of
fluids.
[0002] Furthermore the present invention relates to
diketopyrrolopyrrole analogues of the general formula II, which are
intermediates in the process for the preparation of
diketopyrrolopyrroles of the formula I and can be used as crystal
growth regulators.
[0003] DPP Compounds of the formula 2
[0004] are known:
[0005] Compounds of the formula X in which Y.sup.1 and Y.sup.2
denote hydrogen and Y.sup.3 and Y.sup.4 denote identical or
different isocyclic or heterocyclic aromatic radicals are known as
red pigments from EP-B-61,426.
[0006] U.S. Pat. No. 5,973,146 relates to aminated diketobis(aryl
or heteroaryl)pyrrolo-pyrroles and their use as photoconductive
substances.
[0007] EP-A-1 087005 relates to fluorescent diketopyrrolopyrroles
of the formula I' 3
[0008] wherein R.sub.1' and R.sub.2', independently from each
other, stand for C.sub.1-C.sub.25-alkyl, allyl which can be
substituted one to three times with C.sub.1-C.sub.3alkyl or
Ar.sub.3', --CR.sub.3'R.sub.4'--(CH.su- b.2).sub.m--Ar.sub.3',
wherein R.sub.3' and R.sub.4' independently from each other stand
for hydrogen or C.sub.1-C.sub.4alkyl, or phenyl which can be
substituted one to three times with C.sub.1-C.sub.3 alkyl,
Ar.sub.3' stands for phenyl or 1- or 2-naphthyl which can be
substituted one to three times with C.sub.1-C.sub.8alkyl,
C.sub.1-C.sub.8alkoxy, halogen or phenyl, which can be substituted
with C.sub.1-C.sub.8alkyl or C.sub.1-C.sub.8alkoxy one to three
times, and m' stands for 0, 1, 2, 3 or 4, and wherein
C.sub.1-C.sub.25alkyl or --CR.sub.3'R.sub.4
--(CH.sub.2).sub.m'--Ar.sub.3', preferably C.sub.1-C.sub.25-alkyl,
can be substituted with a functional group capable of increasing
the solubility in water such as a tertiary amino group,
--SO.sup.3.sup.-, or PO.sub.4.sup.2-, Ar.sub.1' and Ar.sub.2',
independently from each other, stand for an aryl or heteroaryl
group. The DPP compounds can be used for the preparation of inks,
colorants, pigmented plastics for coatings, non-impact-printing
material, color filters, cosmetics, or for the preparation of
polymeric ink particles, toners, dye lasers and electroluminescent
devices. EP-A-1087006 describes electroluminescent devices
comprising the DPP compounds of formula (I'). The DPPs exemplified
in EP-A-1087005 and EP-A-1087006 are symmetrically substituted at
the nitrogen atoms of the DPP basic unit.
[0009] EP-A-499 011 discloses organic electroluminescent elements,
comprising a compound of formula X wherein Y.sup.3 and Y.sup.4 are
independently of each other a 3-pyridyl or 4-pyridyl residue or a
substituted or unsubstituted phenyl group and Y.sup.1 and Y.sup.2
are independently of each other hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.3-C.sub.18-alkenyl or a phenylalkyl group having 1 to 5
carbon atoms in the alkyl. The exemplified DPPs,
2,5-dihydro-2,5-dimethyl-3,6-di-
phenylpyrrolo[3,4-c]pyrrole-1,4-dione and
2,5-dihydro-2,5-dimethyl-3,6-di(-
2'-methoxyphenyl)pyrrolo[3,4-c]pyrrole-1,4-dione (example 8 and 10,
respectively), are symmetrically substituted at the nitrogen atoms
of the DPP basic unit.
[0010] WO 98/33862 describes the use of a DPP-compound of formula
4
[0011] as a guest molecule in electroluminescent devices [example
B2].
[0012] EP-A-811 625 discloses DPP compounds of the formula 5
[0013] wherein y.sup.11 is a quinacridone or DPP radical.
[0014] WO96/08537 relates to a process for preparing N-methylated
organic pigments.
[0015] EP-A-467 846 relates to electrochromic compositions
containing at least one DPP derivative.
[0016] The DPP derivatives are symmetrically substituted at the
nitrogen atoms of the DPP basic unit or one nitrogen atom is
substituted by hydrogen and the other nitrogen is substituted by a
group (CH.sub.2).sub.p-L, wherein p is an integer of 1 to 6 and L
is a sulfonic acid, a phosphonic acid, a carboxylic acid group or a
salt thereof, or an ammonium group.
[0017] WO98/25927 relates to liquid crystalline
diketopyrrolopyrroles, which are symmetrically substituted at the
nitrogen atoms of the DPP basic unit.
[0018] The compounds of the above-mentioned general formula X can
be prepared by various known processes:
[0019] According to the process described in EP-B-61,426, a nitrile
of the formula Y.sup.3--CN is reacted, if desired together with a
nitrile of the formula Y.sup.4--CN, with bromoacetic ester and
zinc, a compound of the above-mentioned formula where
y.sup.1=y.sup.2H being formed. Better yields are obtained if 2 mol
of the nitrile Y.sup.3--CN or the nitrile mixture
Y.sup.3--CN/Y.sup.4--CN are reacted in a manner known per se with 1
mol of a diethyl succinate in an organic solvent in the presence of
a strong base at elevated temperature, cf. EP-B-94,911.
[0020] U.S. Pat. No. 4,585,878 relates to N-subsbtuted
1,4-diketopyrrolo[3,4-c]pyrroles of the above-mentioned general
formula in which y.sup.3 and Y.sup.4 are isocyclic aromatic or
heterocyclic aromatic radicals, in particular unsubstituted or
substituted phenyl or naphthyl, and y.sup.1 and y.sup.2 are
independently of one another alkyl, alkoxycarbonyl, phenyl, benzoyl
or benzyl, which are suitable for dyeing high molecular weight
organic material.
[0021] The compounds of the above-mentioned formula are prepared
(a) by reacting the compound of the formula 6
[0022] with a compound containing the radicals y.sup.1 and/or
y.sup.2 as leaving groups, in an organic solvent, or
[0023] (b) by reacting 2 moles of a compound of the formula 7
[0024] or one mole each of the compounds of the formulae (XI) and
(XII), with 1 mole of a succinic acid diester in the presence of a
base and an organic solvent (cf. J. Chem. Soc. 1976, page 5) and
then dehydrogenating the product. The exemplified DPPs, for example
2,5-dihydro-2,5-dibenzyl-3-
,6-diphenylpyrrolo[3,4-c]pyrrole-1,4-dione and
2,5-dihydro-2,5-bis(4'-chlo-
rophenyl-3,6-di(4'-chlorophenylpyrrolo[3,4c]pyrrole-1,4-dione
(example 8 and 10, respectively), are symmetrically substituted at
the nitrogen atoms of the DPP basic unit.
[0025] U.S. Pat. No. 5,354,869 relates to
3,6-bis-(2'-methoxyphenyl)-2,5-d-
ihydro-2,5-dimethyl-pyrrolo[3,4-C]pyrrole-1,4-dione and its use as
storage media in optical memories. Described is also a process for
the preparation of the compounds of the general formula X which
consists in reacting furanofurandione of the general formula 8
[0026] with a primary amine of the general formula Y.sup.1NH.sub.2
or with a mixture of primary amines Y.sup.1NH.sub.2/N.sup.2NH.sub.2
wherein Y.sup.1, Y.sup.2, Y.sup.3 and Y.sup.4 denote hydrogen,
aromatic radicals, heteroaromatic radicals, heterocyclic radicals
or other non-water-solubilising radicals. The exemplified DPPs, for
example
2,5-dihydro-2,5-diphenyl-3,6-diphenylpyrrolo[3,4-c]pyrrole-1,4-dione
and
2,5-dihydro-2,5-bis(4'-methylphenyl-3,6-diphenylpyrrolo[3,4-c]pyrrole-1,4-
-dione (example 13 and 14, respectively), are symmetrically
substituted at the nitrogen atoms of the DPP basic unit. In Liebigs
Ann. 1996, 679-682H. Langhals et al. disclose the synthesis of
N-arylpyrrolopyrrolediones. 9
[0027] Condensation of 1 with aniline yields the intermediate 2
[yield: 15.6%] as an orange powder with a weak yellow solid state
fluorescence. The intermediate 2 was condensed with
para-t-butylaniline yielding the unsymmetric substituted dye 3
[yield: 2.5%]. The overall yield of the disclosed synthesis is very
low.
[0028] In view of the above-mentioned state of the art it is the
object of the present invention to provide a new process for the
preparation of diketopyrrolopyrroles which in particular make it
possible to obtain DPPs which are unsymmetrically substituted at
the nitrogen atoms of the DPP basic unit in an acceptable
yield.
[0029] This object has surprisingly been solved by a process for
the preparation of diketopyrrolopyrroles of the general formula
10
[0030] comprising reacting a compound of the formula 11
[0031] with a primary amine of the formula A.sup.4-NH.sub.2
(III),
[0032] wherein A.sup.1 and A.sup.2 are C.sub.1-C.sub.18alkyl,
C.sub.2-Clsalkenyl, C.sub.2-C.sub.18alkynyl, C.sub.5-C-cycloalkyl,
C.sub.5-C.sub.8cycloalkenyl, aryl or heteroaryl, A.sup.3 is
hydrogen, C.sub.1-C.sub.18alkyl, cyanomethyl, Ar.sup.3,
--CR.sup.30R.sup.31--(CH.su- b.2).sub.M--Ar.sup.3 or Y--R.sup.32,
wherein R.sup.30 and R.sup.31 independently of each other stand for
hydrogen or C.sub.1-C.sub.4alkyl, or phenyl which can be
substituted up to three times with C.sub.1-C.sub.3alkyl, Ar.sup.3
stands for aryl, C.sub.5-C.sub.8cycloalkyl- ,
C.sub.5-C.sub.8cycloalkenyl or heteroaryl, which can be substituted
one to three times with C.sub.1-Cialkyl, C.sub.1-C.sub.8alkoxy,
halogen or phenyl, which can be substituted with
C.sub.1-C.sub.8alkyl or C.sub.1-C.sub.8alkoxy one to three times,
and m stands for 0, 1, 2, 3 or 4, Y is --C(O)--, --C(O)O--,
--C(O)NH-- or --SO.sub.2--, --SO.sub.2NH-- and R.sup.32 is
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkoxy,
--NH--C.sub.1-C.sub.18alkyl, Ar.sup.3, or aralkyl, and A.sup.4 is
C.sub.1-C.sub.16alkyl or Ar.sup.3.
[0033] The reaction between the compound of the general formula II
and the primary amine or the mixture of primary amines is carried
out in a suitable inert solvent or dispersant.
[0034] Suitable solvents or dispersants are, for example, ethers,
in particular those having 2 to 8 carbon atoms in the molecule,
such as, for example, diethyl ether, methyl ethyl ether,
di-n-propyl ether, diisopropyl ether, methyl n-butyl ether, methyl
tert-butyl ether, ethyl n-propyl ether, di-n-butyl ether,
tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane,
bis-B-methoxyethyl ether; oligoethylene glycol dimethyl ethers,
such as, for example, pentaglyme; aliphatic hydrocarbons, such as,
for example, hexane, heptane, low- and high-boiling petroleum
ethers; cycloaliphatic hydrocarbons, such as, for example,
cyclohexane, methylcyclohexane, tetralin, decalin; aromatic
hydrocarbons, such as, for example, benzene, toluene, o-, m- and
p-xylene, ethylbenzene; halogenated aliphatic or aromatic
hydrocarbons, such as, for example, methylene chloride, chloroform,
carbon tetrachloride, chlorobenzene, dichlorobenzene; nitriles,
such as, for example, acetonitrile; amides, such as, for example,
dimethylformamide, dimethylacetamide, N-methylpyrrolidone;
hexamethylphosphoric triamide; and sulfoxides, such as, for
example, dimethyl sulfoxide. Mixtures of various solvents can also
be used.
[0035] The reaction is preferably carried out in a dipolar or
non-polar aprotic solvent. Examples of preferred aprotic solvents
are: dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric
triamide, sulfolane, N-methylpyrrolidone, tetramethylurea,
acetonitrile, ethylene glycol dimethyl ether, ethylene glycol
diethyl ether, diethylene glycol dimethyl ether and triethylene
glycol dimethyl ether, nitromethane,
1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU),
1,3-dimethyl-2-imidazolidinone, benzonitrile, nitrobenzene,
chloroform, carbon tetrachloride and methylene chloride.
Particularly preferred aprotic solvents are chloroform, carbon
tetrachloride and methylene chloride, of which chloroform is
particularly preferred.
[0036] The reaction between the compound of the general formula II
and the primary amine III is carried out in the presence of a
dehydrating agent. Examples of suitable dehydrating or
water-eliminating agents of this type are: N,N'-disubstituted
carbodiimides, in particular if they contain at least one secondary
or tertiary alkyl radical, such as, for example, diisopropyl-,
dicyclohexyl- or N-methyl-N'-tert.-butylcarbodiimide (cf. "The
Chemistry of Ketenes, Allenes and Related Compounds", Part 2,
Editor: S. Patai, John Wiley & Sons 1980, 722-753).
Dicyclohexylcarbodiimide is particularly suitable.
[0037] The reaction between the compound of the formula II and the
primary amine III can be carried out, for example, at temperatures
from -10.degree. C. up to the boiling point of the solvent or
solvent mixture used. In many cases it is carried out at -10 to
30.degree. C. and preferably at room temperature. 0.9 to 1.4 mol,
preferably 1.0 to 1.3 mol of the primary amine III are in general
employed per mole of compound of the general formula II. The
reaction can be catalyzed by adding a strong non-aqueous acid such
as trifluoroacetic acid.
[0038] The primary amines III are known or can be easily prepared
by the methods known for the preparation of these class of
compound.
[0039] The starting compound of the formula II, wherein A.sup.3 is
different from a hydrogen atom, is obtained by reacting a compound
of the formula 12
[0040] with a compound of the formula A.sup.3-X (V), wherein
A.sup.1, A.sup.2 and A.sup.3 have the meanings as given above and X
is a leaving group. The reaction between the compound of the
general formula IV and the compound of the formula V is carried out
in a suitable inert solvent or dispersant such as tetrahydrofuran
or diethyl ether, in the presence of a base such as sodium hydride
at a temperature ranging from 20.degree. C. to the boiling point of
the solvent. The term "eaving group" means a group, such as iodine,
bromine or chlorine, benzene- or p-toluenesulfonate. Processes for
the introduction of A.sup.3 into compounds of the formula IV are
described, for example, in U.S. Pat. No. 4,585,878.
[0041] Suitable alkylating agents are, for example, alkyl halides,
in particular alkyl iodides, alkyl esters, in particular alkyl
esters of sulfonic acids, such as, for example, alkyl esters of
benzene- or p-toluenesulfonic acid. Suitable arylating agents are
for example iodoaryl compounds such as iodobenzene.
[0042] The starting compound of the formula IV is obtained by
heating a compound of the formula 13
[0043] in an inert solvent, wherein A.sup.1 and A.sup.2 have the
meanings as given above and R is C.sub.1-C.sub.18alkyl, in
particular C.sub.1-C.sub.4alkyl, aryl, in particular phenyl, or
aralkyl, in particular benzyl, which can be substituted one to
three times with C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxy, or
halogen. Examples of inert solvents include, but are not limited to
aromatic solvents, like biphenyl, para-, meta or ortho-terphenyl,
dibenzyltoluene, .alpha.-methyl- or .beta.-methylnaphthalene,
cyclic carbonates, like 1,3-dioxolan-2-one, ketones, like
acetophenone or benzophenone, .gamma.-butyrolactone and ethylene
glycols, like Phe-Cellosolve or Bu-Cellosove, or mixtures thereof,
in particular mixtures of di- and triarylethers (Dowtherm A.RTM.).
In a preferred embodiment the compound of the formula VI is
dissolved in Dowtherm A.RTM. and heated for about 0.5 to 240 hours
at a temperature of 220 to 260.degree. C., preferably
230-240.degree. C.
[0044] The present invention is also directed to the compounds of
the formula VI which are novel intermediates in the synthesis of
the diketopyrrolopyrroles of the formula I and the
diketopyrrolopyrrole analogues of the formula II, respectively.
[0045] The starting compound of the formula VI Is obtained by
reacting a compound of the formula 14
[0046] with an ester of the formula A.sup.2-CO.sub.2R (VIII) in the
presence of a base, such as for example sodium
tert.-amylate/tert.-amylal- cohol at a temperature ranging from
25.degree. C. to the boiling point of the solvent, wherein R.
A.sup.1 and A.sup.2 have the meanings as given above.
[0047] The starting compounds of the formula VII are known or can
be prepared in analogy to processes described in U.S. Pat. No.
4,681,971, U.S. Pat. No. 4,749,795, U.S. Pat. No. 4,720,305 and
U.S. Pat. No. 4,659,775.
[0048] Alternatively, compounds of the formula 15
[0049] wherein A.sup.3 is different from a hydrogen atom and is in
particular aryl, can be prepared by a copper catalyzed
decomposition of diazoacetates in the presence of enaminoamides (G.
Maas, A. Muller, J. prakt. Chem. 340 (1998) 315-322): 16
[0050] The compounds of the formula VII, wherein A.sup.3 is
different from a hydrogen atom and is in particular aryl, can be
reacted to compounds of the formula I as described above. 17
[0051] Furthermore, the present invention relates to novel
diketopyrrolopyrroles of the general Formula 18
[0052] wherein A.sup.1, A.sup.2 and A.sup.3 have the meanings as
given above and A.sup.4 is Ar.sup.3, wherein preferably A.sup.4 is
different from A.sup.3.
[0053] The DPPs of the general formula I show a high heat
stability, a good solubility in polymers, hydrocarbon based fuels,
lubricants, and water, a high light stability, and the ability to
be used in plastics, especially polyamides, without decomposition
and loss of lightfastness, and in paints; and can show photo- and
electroluminescence as well as solid state fluorescence.
[0054] The residues A.sup.1 and A.sup.2 are in general selected
from C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.18alkenyl,
C.sub.2-C.sub.18alkynyl, C.sub.5-C.sub.8cycloalkyl, such as
cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, in particular
cyclohexyl, C.sub.5-C.sub.8cycloalkenyl, such as cyclopentenyl,
cyclopentadienyl and cyclohexenyl, in particular cyclohex-3-enyl,
aryl and heteroaryl.
[0055] Diketopyrrolopyrroles, wherein A.sup.1 and A.sup.2 are
radicals of the formula 19
[0056] R.sup.1 and R.sup.2 are independently of each other
hydrogen, halogen, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkoxy,
C.sub.1-C.sub.18alkylmercapto, di(C.sub.1-C.sub.18alkyl)amino,
C.sub.1-C.sub.18alkylamino, C.sub.1-Ciaalkoxycarbonyl,
C.sub.1-C.sub.18alkylaminocarbonyl.sub.1--CN, --NO.sub.2,
trifluoromethyl, C.sub.5-Ccycloalkyl,
--C.dbd.N--(C.sub.1-C.sub.18alkyl), phenyl, 20
[0057] imidazolyl, pyrrazolyl, triazolyl, piperazinyl, pyrrolyl,
oxazolyl, benzoxazolyl, benzothiazolyl, benzimidazolyl,
morpholinyl, piperidinyl or yr --S.sub.2X.sup.9; wherein X.sup.5
and x.sup.6 are hydrogen, linear or branched C.sub.1-10-alkyl,
C.sub.5-10-cycloalkyl or C.sub.6-10-aryl, X.sup.7 is hydrogen,
linear or branched C.sub.1-10-alkyl, C.sub.5-10-cycloalkyl or
C.sub.6-10-aryl, X.sup.9 is hydrogen, linear or branched
C.sub.1-10-alkyl, C.sub.5-10-cycloalkyl, C.sub.7-10-aralkyl,
C.sub.6-10-aryl or --NX.sup.10X.sup.11, wherein X.sup.10 and
X.sup.11 are hydrogen, linear or branched C.sub.1-10-alkyl,
C.sub.7-10-aralkyl or C.sub.6-10-aryl, G is --CH.sub.2--,
--CH(CH.sub.3)--, --C(CH.sub.3).sub.2--, --CH.dbd.N--, --N.dbd.N--,
--O--, --S--, --SO--, --SO.sub.2--, --CONH-- or --NR.sup.7--,
R.sup.3 and R.sup.4 are independently of each other hydrogen,
halogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.18alkoxy or --CN,
R.sup.5 and R.sup.6 are independently of each other hydrogen,
halogen or C.sub.1-C.sub.6alkyl, and R.sup.7 is 21
[0058] wherein R.sup.1 and R.sup.2 are independently of each other
hydrogen, chloro, bromo, C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.6alkylamino, phenyl or CN, G
is --O--, --NR.sup.7--, --N.dbd.N-- or --SO.sub.2--, R.sup.3 and
R.sup.4 are hydrogen, and R.sup.7 is hydrogen, methyl or ethyl are
further preferred and diketopyrrolopyrrole analogues, wherein
A.sup.1 and A.sup.2 are radicals of the formula 22
[0059] wherein R.sup.1 and R.sup.2 are independently of each other
hydrogen, methyl, tert-butyl, chloro, bromo, phenyl or CN are
particularly preferred for the preparation of inks, colorants,
pigmented plastics for coatings, non-impact-printing material,
color filters, cosmetics, polymeric ink particles, toners.
[0060] In the case of electroluminescence applications the
following residues are preferred for A.sup.1 and A.sup.2: 2324
[0061] wherein R.sup.21, R.sup.22, R.sup.23, R.sup.25 and R.sup.26
are independently of each other hydrogen, C.sub.1-C.sub.8alkyl, a
hydroxyl group, a mercapto group, C.sub.1-C.sub.8alkoxy,
C.sub.1-C.sub.8alkylthio, halogen, halo-C.sub.1-C.sub.8alkyl, a
cyano group, an aldehyde group, a ketone group, a carboxyl group,
an ester group, a carbamoyl group, an amino group, a nitro group, a
silyl group or a siloxanyl group and R.sup.24 is a
C.sub.1-C.sub.6alkyl group. Preferably R.sup.21, R.sup.22,
R.sup.23, R.sup.25 and R.sup.26 are independently of each other
hydrogen, C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxy or
C.sub.0-C.sub.8alkylthio, wherein the following residues are
particularly preferred: 2526
[0062] The residue A.sup.3 is in general selected from hydrogen,
C.sub.1-C.sub.18alkyl, eyanomethyl, Ar.sup.3,
--CR.sup.30R.sup.31--(CH.su- b.2).sub.m--Ar.sup.3 or Y--R.sup.32,
wherein R.sup.30 and R.sup.31 independently of each other stand for
hydrogen or C.sub.1-C.sub.4alkyl, or phenyl which can be
substituted up to three times with C.sub.1-C.sub.3alkyl, Ar.sup.3
stands for aryl, in particular phenyl or 1- or 2-naphthyl,
C.sup.5-C.sub.8cycloalkyl, such as cyclopentyl, cyclohexyl,
cyclohoptyl and cyclooctyl, in particular cyclohexyl,
C.sub.5-C.sub.8cycloalkenyl, in particular cyclopentenyl,
cyclopentadienyl and cyclohexenyl, or heteroaryl, which can be
substituted one to three times with C.sub.1-C.sub.8alkyl,
C.sub.1-C.sub.8alkoxy, halogen or phenyl, which can be substituted
with C.sub.1-C.sub.8alkyl or C.sub.1-C.sub.8alkoxy one to three
times, and m stands for O. 1, 2, 3 or 4, Y is --C(O)--, --C(O)O--,
--C(O)NH--, --SO.sub.2NH-- or --SO.sub.2-- and e3 is
C.sub.1-C.sub.18alkyl, Ar.sup.3, or aralkyl.
[0063] A.sup.3 is preferably hydrogen, C.sub.1-C.sub.8alkyl such as
methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl,
tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl,
n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetiamethylbutyl and
2-ethylhexyl, Y--R.sup.32 wherein Y is --C(O)-- and R.sup.32 is
27
[0064] wherein R.sup.40 is C.sub.1-C.sub.4alkyl,
--O--C.sub.1-C.sub.4alkyl- , or --S--C.sub.1-C.sub.4alkyl and
--(CH.sub.2).sub.m--Ar wherein m is 1 and Ar is a group of the
formula 28
[0065] which can be substituted one to three times with
C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxy, halogen or phenyl.
Examples of preferred residues Ar are 29
[0066] wherein R.sup.50 and R.sup.51 are independently of each
other methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl,
isobutyl, tert.-butyl, methoxy, ethoxy, isopropoxy, tert.-butoxy or
chlorine.
[0067] The residue A.sup.4 is in general selected from
C.sub.1-C.sub.18alkyl or Ar.sup.3, in particular Ar.sup.3, wherein
A.sup.4 is preferably 30
[0068] which can be substituted one to three times with
C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxy, halogen or phenyl.
[0069] Moreover, the present invention relates to
diketopyrrolopyrrole analogues of the formula 31
[0070] wherein A.sup.1, A.sup.2 and A.sup.3 have the meanings as
given above, with the proviso that
3,5,6-triphenyl-1H-furo[3,4c]pyrrol-1,4-(5H)- -dion is
excluded.
[0071] The diketopyrrolopyrrole analogues of the formula II are
intermediates in the process for the preparation of the
diketopyrrolopyrroles of the formula I and can be used as crystal
growth regulators, wherein the term "regulating the crystal growth"
refers to controlling the synthesis of pigment particles to have a
suitable pigmentary size and/or a narrow particle size distribution
as well as directing the growth of the crystals to generate
particles of a specifically desired shape, such as platelet,
needle, cubic, leaflet, prismatic and other geometric forms and/or
of a specifically desired rheology. Consequently, the better
control of the crystal growth allows gaining samples with a
narrower particle size distribution and/or a better crystal shape,
or both together. The effect can be influenced by the chemical
structure of the organic pigment, the selection of the reaction
media and the concentration and chemical structure of the inventive
particle growth regulator.
[0072] Hence, a further aspect of the instant invention is directed
to pigment compositions comprising a primary pigment and from about
0.1-20% of the diketopyrrolopyrrole analogue of the formula II
(including 3,5,6-triphenyl-1H-furo[3,4-c]pyrrole-1,4-(5H)-dione),
based on primary pigment weight. Preferred concentrations range
from 1.0 to 10.0%, by weight of primary pigment. Although DPPs are
preferred as primary pigment, the use of diverse pigment moieties
is likewise available where the respective pigments are color
compatible. Examples of applicable organic primary pigments are:
anthraquinone, phthalocyanine, perinone, perylene, dioxazine,
diketopyrrolopyrrole, thioindigo, Isoindoline, isoindolinone,
quinacridone, quinacridonequinone, flavanthrone, indanthrone,
anthrapyrimidine or quinophthalone pigments, and solid solutions
comprising these pigments. Pigments having good heat resistance and
high transparency are especially suitable. Preferred organic
pigments are quinacridones, phthalocyanines, anthraquinones,
perylenes, diketopyrrolopyrroles, isoindolinones and
indanthrones.
[0073] When the pigment compositions are prepared, the
diketopyrrolopyrrole analogues of the formula II can be added
during the pigment synthesis, during the fine dispersion process,
before or after a finishing process by methods well-known in the
art.
[0074] The diketopyrrolopyrrole analogues of formula II are in
particular used as crystal growth regulator in a process for the
direct preparation of DPP compounds of the formula 32
[0075] wherein X.sup.1 and X.sup.2 independently of each other are
an unsubstituted or substituted isocyclic or heterocyclic aromatic
radical. Said process comprises (a) heating an appropriate molar
ratio of a disuccinate with a nitrile of the formula (II)
X.sup.1--CN (XI)
[0076] or of the formula (III)
X.sup.2--CN (XII)
[0077] or with mixtures of said nitriles, in an organic solvent and
in the presence of a strong base, to form a product,
[0078] (b) conditioning of the intermediate condensation product
obtained in step (a) in water or a mixture of water and a
water-miscible solvent, optionally in the presence of an inorganic
acid to form the compound of formula (X), and
[0079] (c) optionally conditioning of the product obtained in step
(b) in an aprotic solvent, wherein a diketopyrrolopyrrole analogue
of formula II is added in the heating step (a), the conditioning
step (b) or (c).
[0080] Due to the presence of crystal growth regulors DPP particles
exhibiting a higher opacity/hiding power than commercial pigments
synthesized without growth controllers are obtained.
[0081] Hence, the present invention relates also to pigment
compositions' comprising
[0082] a) a 1,4-diketopyrrolo[3,4-c]pyrrole of the formula X;
and
[0083] b) an effective crystal growth directing amount of a
compound of formula II.
[0084] The particle growth regulator is present in an amount of
between 0.1 and 10 weight %, based on the weight of the
diketopyrrolopyrrole. A more useful range of particle growth
regulator is from 0.5% to 4%, In particular 0.5% to 2% by weight of
the particle growth regulator.
[0085] The expressions "direct" or "directly", when used herein to
describe a preparatory process for a pigmentary product, means that
the specific surface area of the pigmentary product will be within
the range which makes it suitable for use as a pigment with
specific desired properties. In order for the
1,4-diketopyrrolo[3,4-c]pyrroles of formula (I) to be suitable for
direct use as a pigment, the surface area of the reaction product
should be at least 15 meters.sup.2/gram, for example in the range
of from about 15 to about 50 m.sup.2/gram, preferably from about 20
to 50 m.sup.2/gram. The surface area can be measured by nitrogen
absorption or another suitable method.
[0086] The radicals X.sup.1 and x.sup.2 may be the same or
different, but are preferably identical. X.sup.1 and X.sup.2 as
isocyclic aromatic radicals are preferably monocyclic to
tetracyclic radicals, most preferably monocyclic or bicyclic
radicals such as phenyl, diphenyl, naphthyl and the like.
[0087] Heterocyclic aromatic radicals X.sup.1 and X.sup.2 are
preferably monocyclic to tricyclic radicals.
[0088] These radicals may be entirely heterocyclic or may contain a
heterocyclic ring and one or more fused benzene rings, and the
cyano group can be linked both to the heterocyclic and to the
isocyclic moiety respectively. Examples of heterocyclic aromatic
radicals are pyridyl, pyrimidyl, pyrazinyl, triazinyl, furyl,
pyrrolyl, thiophenyl, quinolyl, cumarinyl, benzfuranyl,
benzimidazolyl, benzoxazolyl, dibenzfuranyl, benzothiophenyl,
dibenzothiophenyl, indolyl, carbazolyl, pyrazolyl, imidazolyl,
oxazolyl, isoxazolyl, thiazolyl, indazolyl, benzthiazolyl,
pyridazinyl, cinnolyl, quinazolyl, quinoxalyl, phthalazinyl,
phthalazindionyl, phthalamidyl, chromonyl, naphtholactamyl,
quinolonyl, ortho-sulfobenzimidyl, maleinimidyl, naphtharidinyl,
benzimidazolonyl, benzoxazolonyl, benzthiazolonyl,
benzthiazothionyl, quinazolonyl, quinoxalonyl, phthalazonyl,
dioxopyrimidinyl, pyridonyl, isoquinolonyl, isoquinolinyl,
isothiazolyl, benzisoxazolyl, benzisothiazolyl, indazolonyl,
acridonyl, quinazolindionyl, quinoxalindionyl, benzoxazindionyl,
benzoxazinonyl and naphthalimidyl. Both the isocyclic and the
heterocyclic aromatic radicals may contain the customary
non-watersolubilising substituents such as those described in U.S.
Pat. No. 6,057,449.
[0089] Pyrrolo[3,4-c]pyrroles of the formula X, in which X.sup.1
and X.sup.2 independently of one another are a group of the formula
33
[0090] in which X, X.sup.32 and X.sup.33 independently of one
another are hydrogen, halogen, C.sub.0-C.sub.24alkyl,
C.sub.1-C.sub.6alkoxy, C.sub.1-C.sub.18alkylthio,
C.sub.1-C.sub.18alkylamino, di(C.sub.1-C.sub.18alkyl)amino, --CN,
--NO.sub.2, phenyl, trifluoromethyl, C.sub.5-C.sub.6cycloalkyl,
[0091] --C.dbd.N--(C.sub.1-C.sub.24alkyl), 34
[0092] imidazolyl, pyrazolyl, triazolyl, piperazinyl, pyrrolyl,
oxazolyl, benzoxazolyl, benzothiazolyl, benzimidazolyl,
morpholinyl, piperidinyl or pyrrolidinyl, T.sub.2 is --CH.sub.2--,
--CH(CH.sub.3)--, --C(CH.sub.3).sub.2--, --CH.dbd.N--, --N.dbd.N--,
--O--, --S--, --SO--, --SO.sub.2-- or --NX.sup.38-, X.sup.34 and
X.sup.35 independently of one another are hydrogen, halogen,
CO.sub.16-alkyl, Clalkoxy or --CN, X.sup.36 and X3 independently of
one another are hydrogen, halogen or C.sub.1-6-alkyl and X.sup.38
is hydrogen or C.sub.1-C.sub.6-alkyl; are preferred and DPPs of the
formula X, in which xt and X.sup.2 are independently of each other
a group of the formula 35
[0093] in which X.sup.31 and X.sup.32 independently of one another
are hydrogen, methyl, tert-butyl, chlorine, bromine, CN or phenyl
are especially preferred.
[0094] In particular, the starting materials employed are nitriles
of the formula 36
[0095] wherein each of X.sup.20, X.sup.21 and X.sup.22,
independently of one another, is hydrogen, fluorine, chlorine,
bromine, carbamoyl, cyano, trifluoromethyl,
C.sub.2-10-alkylcarbamoyl, C.sub.1-10-alkyl, C.sub.1-10-alkoxy,
C.sub.1-10-alkylmercapto, C.sub.2-10-alkoxycarbonyl,
C.sub.2-10-alkanoylamino, C.sub.1-10-monoalkylamino,
C.sub.1-20-dialkylamino, phenyl or phenoxy, phenylmercapto,
phenoxycarbonyl, phenylcarbamoyl or benzoylamino, each
unsubstituted or substituted by halogen, C.sub.1-4-alkyl or
C.sub.1-4alkoxy, with the proviso that at least one of X.sup.20,
X.sup.21 or X.sup.22 is hydrogen.
[0096] Preferably, the starting materials employed are nitriles of
the formula XIa, wherein X.sup.20 is hydrogen and both X2' and
X.sup.22 are hydrogen, or one of X.sup.21 or X.sup.22 is chlorine,
bromine, C.sub.1-4-alkyl, cyano, C.sub.1-4-alkoxy, or is phenyl,
phenoxy, carbamoyl or C.sub.1-4-alkylcarbamoyl, each unsubstituted
or substituted by chlorine or methyl, or is phenylcarbamoyl which
is unsubstituted or substituted by chlorine, methyl or methoxy, and
the other is hydrogen.
[0097] In a further preferred embodiment of the present process
only one nitrile of formula (XI) or of formula (XII) is used.
[0098] A preferred embodiment of the present invention concerns a
process wherein X.sup.1 and X.sup.2, each independently of the
other, are phenyl or said phenyl substituted by one or two chlorine
atoms, by one or two methyl groups, by methoxy, by trifluoromethyl,
by cyano, by methpxycarbonyl, by methyl, by tert-butyl, by
dimethylamino or by cyanophenyl; naphthyl, biphenylyl; pyridyl or
said pyridyl substituted by amyloxy; furyl or thienyl, such as
phenyl, 3-chlorophenyl, 4-chlorophenyl, 3,5-dichlorophenyl,
4-methylphenyl, 4-methoxyphenyl, 3-trifluoromethylphenyl,
4-trifluoromethylphenyl, 3-cyanophenyl, 4-cyanophenyl,
4-methoxycarbonylphenyl, 4-methylphenyl, 4-tert-butylphenyl,
4-dimethylaminophenyl, 4-(para-cyanophenyl)phenyl, 1-naphthyl,
2-naphthyl, 4-biphenylyl, 2-pyridyl, 6-amyloxy-3-pyridyl, 2-furyl
or 2-thienyl.
[0099] The disuccinates include dialkyl, diaryl or
monoalkyl-monoaryl succinates. The dialkyl and diaryl succinates
may also be asymmetrical. However, it is preferred to use
symmetrical disuccinates, most preferably symmetrical dialkyl
succinates, most preferably symmetrical dialkyl succinates. If a
diaryl or monoaryl-monoalkyl succinate is employed, aryl denotes
preferably phenyl which is unsubstituted or substituted by halogen
such as chlorine, C.sub.1-6-alkyl such as ethyl, methyl, isopropyl
or tert-butyl, or C.sub.1-alkoxy such as methoxy or ethoxy.
[0100] The preferred meaning of aryl is unsubstituted phenyl. If a
dialkyl or monoalkyl-monoaryl succinate is employed, then alkyl may
be unbranched or branched, preferably branched, and may contain
preferably 1 to 18, in particular 1 to 12, more particularly 1 to 8
and more preferably 1 to 5, carbon atoms. Branched alkyl is
preferably sec- or tert-alkyl, for example, isopropyl, sec-butyl,
tert-butyl, tert-amyl and cyclohexyl.
[0101] Examples of disuccinates are dimethyl succinate, diethyl
succinate, dipropyl succinate, dibutyl succinate, dipentyl
succinate, dihexyl succinate, diheptyl succinate, dioctyl
succinate, diisopropyl succinate, di-sec-butyl succinate,
di-tert-butyl succinate, di-tert-amyl succinate,
di-[1,1-dimethylbutyl] succinate, di-[1,1,3,3-tetramethylbutyl]
succinate, di-[1,1-dimethylpentyl] succinate,
di-[1-methyl-ethylbutyl] succinate, di-[1,1-diethylpropyl]
succinate, diphenyl succinate, di-[4-methylphenyl] succinate,
di-[4-chlorophenyl] succinate, monoethyl-monophenyl succinate, and
dicyclohexyl succinate. Most preferably, the starting disuccinate
is diisopropyl succinate.
[0102] Typically, the nitrile and the disuccinate are used in
stoichiometric proportions. It can be advantageous to use the
nitrile to be reacted with the disuccinate in more than only
stoichiometric proportions. The reaction of the disuccinate with
the nitrile is carried out in an organic solvent. Examples of
suitable solvents are primary, secondary or tertiary alcohols
containing 1 to 10 carbon atoms, for example, methanol, ethanol,
n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol,
n-pentanol, 2-methyl-2-butanol, 2-methyl-2-pentanol,
3-methyl-3-pentanol, 2-methyl-2-hexanol, 3-ethyl-3-pentanol,
2,4,4-trimethyl-2-pentanol, or glycols such as ethylene glycol or
diethylene glycol; and also ethers such as tetrahydrofuran or
dioxan, or glycol ethers such as ethylene glycol methyl ether,
ethylene glycol ethyl ether, diethylene glycol monomethyl ether or
diethylene glycol monoethyl ether; as well as dipolar aprotic
solvents such as acetonitrile, benzonitrile, dimethylformamide,
N,N-dimethylacetamide, nitrobenzene, N-methylpyrrolidone; aliphatic
or aromatic hydrocarbons such as benzene or benzene substituted by
alkyl, alkoxy or halogen, for example, toluene, xylene, anisole or
chlorobenzene; or aromatic heterocyclic compounds such as pyridine,
picoline or quinoline. In addition, it is also possible to use the
nitrile of formula (XI) or (XII) simultaneously as solvent if it is
liquid in the temperature range in which the reaction takes place.
Mixtures of the above solvents may also be used. It is convenient
to use 5 to 20 parts be weight of solvent per 1 part by weight of
reactants.
[0103] The process according to the invention is carried out in the
presence of a strong base.
[0104] Suitable strong bases are in particular the alkali metals
themselves such as lithium, sodium or potassium, or alkali metal
amides such as lithium amide, sodium amide or potassium amide, or
alkali metal hydrides such as lithium, sodium or potassium hydride,
or alkaline earth metal alcoholates or alkali metal alcoholates
which are derived preferably from primary, secondary or tertiary
aliphatic alcohols containing from 1 to 10 carbon atoms.
[0105] The preferred strong base is an alkali metal alcoholate, the
alkali metals being preferably sodium or potassium and the
alcoholate being preferably derived from a secondary or tertiary
alcohol, for example, sodium or potassium isopropylate, sodium or
potassium sec-butylate, sodium or potassium tert-butylate and
sodium or potassium tert-amylate.
[0106] The strong base is employed in an amount of preferably from
about 0.1 to about 10 moles, most preferably from about 1.9 to
about 4.0 moles, based on one mole of the disuccinate.
[0107] Regulation in particle size of the
1,4-diketopyrrolo[3,4-c]pyrroles of formula X relative to the
particle size of the unregulated form thereof becomes noticeable
with the inclusion of as little as 0.1% of the particle growth
regulator relative to the weight of the DPP compound of the formula
II. The level of the regulator can be as high as 10% by weight. The
preferred range of particle growth regulator is from 0.5 to 4% by
weight, the most preferred range is from 0.5% to 2% by weight.
[0108] A preferred embodiment is to charge the reaction vessel with
the nitrile and the base and then adding the disuccinate in the
range of the reaction temperature, which addition order has a
particularly advantageous effect on the yield. It is also possible
to add the disuccinate and the nitrile simultaneously to the
base.
[0109] In particular, when using disuccinates containing alkyl
radicals and alcoholates which are derived from lower alcohols such
as methanol, ethanol, n-propanol, isopropanol or tert-butanol, it
may be necessary to remove the lower alcohol formed during the
reaction from the reaction medium continuously in order to obtain
higher yields.
[0110] If an alcohol is used as solvent and an alcoholate as base,
it may prove advantageous to choose an alcohol and alcoholate
having the same alkyl moieties. It may likewise be advantageous if,
in addition, the disuccinate also contains such alkyl groups.
[0111] The conditioning step a) is carried out in water containing
0.0-100.0%, preferably 20.0-50.0% of a water-miscible solvent, at a
conditioning temperature of 1.degree. C. to the reflux temperature,
preferably close to reflux temperature, optionally in the presence
of an inorganic acid.
[0112] In general water-miscible solvents are selected from
water-miscible alcohols, polyols, nitrites, organic acids, amides,
esters, ethers, ketones, amines or a mixture of these solvents.
[0113] Especially suitable water-miscible solvents include
alcohols, in particular C.sub.1-4-alkyl alcohols, such as methanol,
ethanol, n- and isopranol, polyols, like glycols, such as ethylene
glycol, diethylene glycol, ethers, like glycol ethers, such as
ethylene glycol methyl ether, ethylene glycol ethyl ether,
diethylene glycol monomethyl ether or diethylene glycol
monoethylether, tetrahydrofuran (THF) and dioxane, organic acids,
like acetic acid, ketones, like acetone, amines, such as mono-, di-
or trialkylamines, such as propylamine, Isopropylamine,
diethylamine, dipropylamine, diisopropylamine, triethylamine,
tripropylamine, triIsopropylamine, bis(1-methyl)propylamine,
1,1-dimethylethylamine and 2-ethylhexylamine, aromatic amines, such
as aniline, toluidine or phenylene diamine, and mixtures
thereof.
[0114] Suitable inorganic acids are hydrochloric, sulphuric and
phosphoric acid.
[0115] The conditioning step b) is carried out in an aprotic,
water-miscible solvent in the presence of 0.0-99.0% water or in
nonmiscible solvents with high boiling point or mixtures thereof at
a conditioning temperature from 1.degree. C. to the boiling point,
most preferably 10-20.degree. C. below the boiling point of the
solvent.
[0116] Suitable aprotic, water-miscible solvents include
acetonitrile, N-methyl-2-pyrrolidone (NMP), gamma-butyrolactone,
dimethylsulfoxide (DMSO), N,N-dimethylacetamide (DMA),
N,N-dimethylformamide (DMF), and mixtures thereof. Nonmiscible
solvents include diphenylether, such as Dowtherm.RTM. E,
nonmiscible alcohols, such as pentanol, hexanol and heptanol,
nonmiscible aromatic solvents like toluene, xylene,
o-dichlorobenzene, nonmiscible ketones, nonmiscible ethers and
cyclic ethers, nonmiscible amines and aromatic amines, nonmiscible
amides and esters and mixtures thereof.
[0117] The particle growth regulator of formula II can be added in
the heating step (a), the conditioning step (b) or the conditioning
step (c).
[0118] The process is illustrated below in further detail on the
basis of preferred embodiments:
[0119] Process A-1:
[0120] The synthesis of the DPPs of the formula X is done in the
presence of 0.1-20.0%, preferably 0.25-2.0% DPP analogue of the
formula II, wherein the DPP analogue is preferably added at the
beginning or at the end of the DPP synthesis, just before the
conditioning.
[0121] The conditioning is carried out in water containing
0.0-100.0%, preferably 20.0-50.0% of a water-miscible solvent, at a
conditioning temperature of 1.degree. C. to the reflux temperature,
preferably close to reflux temperature.
[0122] Process A-2:
[0123] The synthesis of the DPPs of the formula X is done in the
presence of 0.1-20.0%, preferably 0.25-2.0% of the DPP analogue of
formula II, wherein the DPP analogue of formula II is added at the
beginning or at the end of the DPP synthesis, just before the first
conditioning.
[0124] The first conditioning is carried out in water containing
0.0-100.0%, preferably 20.0-50.0% of a water-miscible solvent at a
conditioning temperature of 1.degree. C. to the reflux temperature,
preferably 0.degree.-40.degree. C., optionally in the presence of
1.0-99.0%, preferably 5.0-20.0% inorganic acid.
[0125] The second conditioning is carried out in an aprotic,
water-miscible solvent in the presence of 0.0-99.0% water at a
conditioning temperature from 1.degree. C. to the boiling point,
most preferably 10-20.degree. C. below the boiling point of the
solvent or in a non-miscible solvent with a high boiling point at a
conditioning temperature from room temperature to the boiling
point, preferably 10-20.degree. C. below the boiling point of the
solvent.
[0126] Process A-3:
[0127] The synthesis of the DPPs of formula X is done without the
addition of a crystal growth regulator of formula II.
[0128] The first conditioning is carried out in water containing
0.0-100.0%, preferably 20.0-50.0% of a water-miscible solvent at a
conditioning temperature of 1.degree. C. to the reflux temperature,
preferably 1040.degree. C., optionally in the presence of
1.0-99.0%, preferably 5.0-20.0% inorganic acid.
[0129] The second conditioning is carried out in an aprotic,
water-miscible solvent in the presence of 0.0-99.0% water at a
conditioning temperature from 1.degree. C. to the boiling point,
most preferably 10-20.degree. C. below the boiling point of the
solvent or in a non-miscible solvent with a high boiling point at a
conditioning temperature from room temperature to the boiling
point, preferably 10-20.degree. C. below the boiling point of the
solvent in the presence of 0.1-20.0%, preferably 0.25-2.0% of the
DPP analogue of formula II.
[0130] Diketopyrrolopyrrole analogues, wherein A.sup.1 and A.sup.2
are radicals of the formula 37
[0131] R.sup.1 and R.sup.2 are independently of each other
hydrogen, halogen, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkoxy,
C.sub.1-C.sub.18alkylmercapto, C.sub.1-C.sub.18alkylamino,
C.sub.1-C.sub.18alkoxyrarbonyl, C.sub.1-C.sub.18alkylaminocarbonyl,
--CN, --NO.sub.2, trifluoromethyl, C.sub.5-C.sub.8cycloalkyl,
--C.dbd.N--(C.sub.1-C.sub.18alkyl), phenyl, 38
[0132] imidazolyl, pyrazolyl, triazolyl, piperazinyl, pyrrolyl,
oxazolyl, benzoxazolyl, benzothiazolyl, benzimidazolyl,
morpholinyl, piperidinyl or pyrrolidinyl, --CONX.sup.5X.sup.6,
--C(O)X.sup.7 or --SO.sub.2X.sup.9; wherein X.sup.5 and X.sup.6 are
hydrogen, linear or branched C.sub.1-10-alkyl,
C.sub.5-10-cycloalkyl or C.sub.6-10-aryl, X.sup.7 is hydrogen,
linear or branched C.sub.1-10-alkyl, C.sub.5-10-cycloalkyl or
C.sub.6-l.sub.0-aryl, X.sup.9 is hydrogen, linear or branched
C.sub.1-10-alkyl, C.sub.5-10-cycloalkyl, C.sub.7-10-aralkyl,
C.sub.6-10-aryl or --NX.sup.10X.sup.11, wherein X.sup.10 and
X.sup.11 are hydrogen, linear or branched C.sub.1-10-alkyl,
C.sub.7-10-aralkyl or C.sub.6-10-aryl,
[0133] G is --CH.sub.2--, --CH(CH.sub.3)--, --C(CH.sub.3).sub.2--,
--CH.dbd.N--, --N.dbd.N--, --O--, --S--, --SO--, SO.sub.2--,
--CONH-- or --NR.sup.7--, R.sup.3 and R.sup.4 are independently of
each other hydrogen, halogen, C.sub.1-C.sub.6alkyl,
C.sub.1-C.sub.18alkoxy or --CN, R.sup.5 and RW are independently of
each other hydrogen, halogen or C.sub.1-C.sub.6alkyl, and R.sup.7
is is hydrogen or C.sub.0-C.sub.6alkyl are preferred, wherein
radicals of the formula 39
[0134] wherein R.sup.1 and R.sup.2 are independently of each other
hydrogen, chloro, bromo, C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.6alkoxy, C.sub.0-C.sub.6alkylamino, phenyl or CN,
--CONX.sup.5X.sup.6, or --SO.sub.2X.sup.9; wherein Xsand Xe are
hydrogen, linear or branched C.sub.1-4-alkyl, X.sup.9 is hydrogen,
linear or branched C.sub.1-4-calkyl, C.sub.7-10 aralkyl,
C.sub.6-10-aryl or --NX.sup.10X.sup.11, wherein X.sup.10 and
X.sup.11 are hydrogen, linear or branched C.sub.1-10-alkyl,
C.sub.7-10-aralkyl or C.sub.6-10-aryl;
[0135] G is --O--, --NR.sup.7--, --N.dbd.N-- or --SO.sub.2--,
[0136] R.sup.3 and R.sup.4 are hydrogen, and
[0137] R.sup.7 is hydrogen, methyl or ethyl are further preferred
and diketopyrrolopyrrole analogues, wherein A.sup.1 and A.sup.2 are
radicals of the formula 40
[0138] wherein R.sup.1 and R.sup.2 are independently of each other
hydrogen, C.sub.1-4-alkyl, such as methyl or tert-butyl, halogen,
such as chloro or bromo, C.sub.1-4-alkoxy or C.sub.1-4-thioalkyl,
phenyl or CN or --SO.sub.2X.sup.9, wherein X.sup.9 is
C.sub.1-4-alkyl, phenyl, benzyl or NX.sup.10X.sup.11, wherein
X.sup.10 and X.sup.11 are hydrogen, C.sub.1-4-alkyl, benzyl or
phenyl are particularly preferred.
[0139] A.sup.3 is preferably hydrogen, C.sub.1-C.sub.8alkyl such as
methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl,
tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl,
n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and
2-ethylhexyl, Y--R.sup.32 wherein Y is --C(O)-- and R.sup.32 is
41
[0140] wherein R.sup.40 is C--C.sub.4alkyl,
--O--C.sub.0-C.sub.4alkyl, or --S--C.sub.1-C.sub.4alkyl and
--(CH.sub.2).sub.m--Ar wherein m is 1 and Ar is a group of the
formula 42
[0141] which can be substituted one to three times with
C.sub.1-C.sub.8alkyl, C.sub.1-C.sub.8alkoxy, halogen or phenyl.
[0142] C.sub.1-C.sub.18alkyl is typically linear or branched--where
possible--and examples of C.sub.1-C.sub.18alkyl are methyl, ethyl,
n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl,
n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl,
n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl,
n-nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl,
hexadecyl, heptadecyl and octadecyl. C.sub.1-C.sub.8alkyl such as
methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl,
tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl,
n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and
2-ethylhexyl is preferred. C.sub.1-C.sub.4alkyl such as methyl,
ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl or
tert.-butyl is particularly preferred. The term
"C.sub.2-C.sub.18alkenyl group" means an unsaturated linear or
branched aliphatic hydrocarbon group containing one or more double
bonds, in particular C.sub.2-8-alkenyl, such as vinyl, allyl,
2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1,3-butadien-2-yl,
2-penten-1-yl, 3-penten-2-yl, 2-methyl-1-buten-3-yl,
2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl and
1,4-pentadien-3-yl.
[0143] The term "C.sub.2-C.sub.18alkynyl group" means an
unsaturated aliphatic hydrocarbon group containing a triple bond,
in particular C.sub.2-C.sub.8-alkynyl such as ethynyl,
1-propyn-1-yl, 2-butyn-1-yl, 3-butyn-1-yl, 2-pentyn-1-yl and
3-pentyn-2-yl.
[0144] Examples of C.sub.1-C.sub.18alkoxy, which can be linear or
branched, are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,
sec.-butoxy, isobutoxy, tert.-butoxy, n-pentoxy, 2-pentoxy,
3-pentoxy, 2,2-dimethylpropoxy, n-hexoxy, n-heptoxy, n-octoxy,
1,1,3,3-tetramethylbutoxy and 2-ethylhexoxy, wherein
C.sub.1-C.sub.4alkoxy such as methoxy, ethoxy, n-propoxy,
isopropbxy, n-butoxy, sec.-butoxy, isobutoxy and tert.-butoxy is
preferred. Examples of C.sub.1-C.sub.18alkylmercapto are the same
groups as mentioned for the alkoxy groups, except that the oxygen
atom of the ether linkage is replaced by a sulphur atom. Examples
and preferences for C.sub.1-C.sub.18alkyl in
C.sub.1-C.sub.18alkylamino and C.sub.1-C.sub.18alkylaminocarbonyl
are the same as mentioned for C.sub.1-C.sub.18alkyl. Examples and
preferences for C.sub.1-C.sub.18alkoxy in
C.sub.1-C.sub.18alkoxycarbonyl are the same as mentioned for
C.sub.1-C.sub.18alkoxy.
[0145] The term "aryl group" is typically C.sub.6-C.sub.24aryl,
such as phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, phenanthryl,
terphenyl, pyrenyl, 2- or 9-fluorenyl or anthracenyl, preferably
C.sub.6-C.sub.12aryl such as phenyl, 1-naphthyl, 2-naphthyl,
4-biphenyl, which may be unsubstituted or substituted.
[0146] The term "aralkyl group" is typically
C.sub.7-C.sub.24aralkyl, such as benzyl, 2-benzyl-2-propyl,
.beta.-phenylethyl, .alpha.,.alpha.-dimethy- lbenzyl,
.omega.-phenylbutyl, .omega.,.omega.-dimethyl-.omega.-phenylbutyl-
, .omega.-phenyldodecyl, .omega.-phenyloctadecyl,
.omega.phenyleicosyl or .omega.-phenyldocosyl, preferably
C.sub.7-C.sub.18aralkyl such as benzyl, 2-benzyl-2-propyl,
.beta.-phenylethyl, .alpha.,.alpha.-dimethylbenzyl,
.omega.-phenylbutyl, .omega.,.omega.-dimethyl-.omega.-phenylbutyl,
.omega.-phenyldodecyl or .omega.-phenyloctadecyl, and particularly
preferred C.sub.7-C.sub.12aralkyl such as benzyl,
2-benzyl-2-propyl, .beta.-phenyl-ethyl,
.alpha.,.alpha.-dimethylbenzyl, .omega.-phenyl-butyl, or
.omega.,.omega.-dimethyl-.omega.-phenyl-butyl, in which both the
aliphatic hydrocarbon group and aromatic hydrocarbon group may be
unsubstituted or substituted.
[0147] Examples of C.sub.5-C.sub.8cycloalkyl are cyclopentyl,
cyclohexyl, cycloheptyl and cyclooctyl, which may be unsubstituted
or substituted. The term "C.sub.5-C.sub.8cycloalkenyl group" means
an unsaturated alicyclic hydrocarbon group containing one or more
double bonds, such as cyclopentenyl, cyclopentadienyl and
cyclohexenyl, which may be unsubstituted or substituted.
[0148] The term "heteroaryl" is a ring with five to seven ring
atoms, wherein nitrogen, oxygen or sulfur are the possible hetero
atoms, and is typically an unsaturated heterocyclic radical with
five to 18 atoms having at least six conjugated .pi.-electrons such
as thienyl, benzo[b]thienyl, dibenzo[b,d]thienyl, thianthrenyl,
furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl,
dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl,
pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl,
indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl,
quinolyl, isoquinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl,
quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, carbolinyl,
benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl,
perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl,
phenothiazinyl, isoxazolyl, furazanyl or phenoxazinyl.
[0149] Examples of a halogen atom are fluorine, chlorine, bromine
and iodine.
[0150] If the above-mentioned substituents can be substituted,
possible substituents are C.sub.1-C.sub.8alkyl, a hydroxyl group, a
mercapto group, C.sub.1-C.sub.8alkoxy, C.sub.1-C.sub.8alkylthio,
halogen, halo-C.sub.1-C.sub.8alkyl, a cyano group, an aldehyde
group, a ketone group, a carboxyl group, an ester group, a
carbamoyl group, an amino group, a nitro group, a silyl group or a
siloxanyl group, The present invention relates also to the use of
the inventive DPP analogues of the general formula I for the
preparation of inks for printing inks in printing processes, for
flexographic printing, screen printing, packaging printing,
security ink printing, intaglio printing or offset printing, for
pre-press stages and for textile printing, for office, home
applications or graphics applications, such as for paper goods, for
example, for ballpoint pens, felt tips, fiber tips, card, wood,
(wood) stains, metal, inking pads or inks for impact printing
processes (with impact-pressure ink ribbons), for the preparation
of colorants for coating materials, for industrial or commercial
use, for textile decoration and industrial marking, for roller
coatings or powder coatings or for automotive finishes, for
high-solids (low-solvent), water-containing or metallic coating
materials or for pigmented formulations for aqueous paints, for the
preparation of pigmented plastics for coatings, fibers, platters or
mold carriers, for the preparation of non-impact-printing material
for digital printing, for the thermal wax transfer printing
process, the ink jet printing process or for the thermal transfer
printing process, and also for the preparation of color filters,
especially for visible light in the range from 400 to 700 nm, for
liquid-crystal displays (LCDs) or charge combined devices (CCDs) or
for the preparation of cosmetics or for the preparation of
polymeric Ink particles, toners, dye lasers, dry copy toners liquid
copy toners, or electrophotographic toners, and electroluminescent
devices.
[0151] Illustrative examples of suitable organic materials of high
molecular weight which can be colored with the inventive
fluorescent DPP analogues of the general formula I are vinyl
polymers, for example polystyrene, poly-.alpha.-methylstyrene,
poly-p-methylstyrene, poly-p-hydroxystyrene,
poly-p-hydroxyphenylstyrene, polymethyl methacrylate and
polyacrylamide as well as the corresponding methacrylic compounds,
poly(methyl) maleate, polyacrylonitrile, polymethacrylonitrile,
polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride,
polyvinylidene fluoride, polyvinyl acetate, polymethyl vinyl ether
and polybutyl vinyl ether; polymers which are derived from
maleinimide and/or maleic anhydride, such as copolymers of maleic
anhydride with styrene; poly(vinyl)pyrrolidone; ABS; ASA;
polyamides; polyimides; polyamidimides; polysulfones; polyether
sulfones; polyphenylene oxides; polyurethanes; polyureas;
polycarbonates; polyarylenes; polyarylene sulfides; polyepoxides;
polyolefins such as polyethylene and polypropylene; polyalkadienes;
biopolymers and the derivatives thereof e.g. cellulose, cellulose
ethers and esters such as ethylcellulose, nitrocellulose, cellulose
acetate and cellulose butyrate, starch, chitin, chitosan, gelatin,
zein; natural resins; synthetic resins such as alkyd resins,
acrylic resins, phenolic resins, epoxide resins, aminoformaldehyde
resins such as urea/formaldehyde resins and melamine/formaldehyde
resin; vulcanized rubber; casein; silicone and silicone resins;
rubber, chlorinated rubber; and also polymers which are used, for
example, as binders in paint systems, such as novolaks which are
derived from C.sub.1-C.sub.6-aldehydes such as formaldehyde and
acetaldehyde and a binuclear or mononuclear, preferably
mononuclear, phenol which, if desired, is substituted by one or two
C.sub.1-Cgalkyl groups, one or two halogen atoms or one phenyl
ring, such as o-, m- or p-cresol, xylene, p-tert.-butylphenol, o-,
m- or p-nonylphenol, p-chlorophenol or p-phenylphenol, or a
compound having more than one phenolic group such as resorcinol,
bis(4-hydroxyphenyl)methane or 2,2-bis(4-hydroxyphenyl)propane; as
well as suitable mixtures of said materials.
[0152] Particularly preferred high molecular weight organic
materials, in particular for the preparation of a paint system, a
printing ink or ink, are, for example, cellulose ethers and esters,
e.g. ethylcellulose, nitrocellulose, cellulose acetate and
cellulose butyrate, natural resins or synthetic resins
(polymerization or condensation resins) such as aminoplasts, in
particular urea/formaldehyde and melamine/formaldehyde resins,
alkyd resins, phenolic plastics, polycarbonates, polyolefins,
polystyrene, polyvinyl chloride, polyamides, polyurethanes,
polyester, ABS, ASA, polyphenylene oxides, vulcanized rubber,
casein, silicone and silicone resins as well as their possible
mixtures with one another.
[0153] It is also possible to use high molecular weight organic
materials in dissolved form as film formers, for example boiled
linseed oil, nitrocellulose, alkyd resins, phenolic resins,
melamine/formaldehyde and urea/formaldehyde resins as well as
acrylic resins.
[0154] Said high molecular weight organic materials may be obtained
singly or in admixture, for example in the form of granules,
plastic materials, melts or in the form of solutions, in particular
for the preparation of spinning solutions, paint systems, coating
materials, inks or printing inks.
[0155] In a particularly preferred embodiment of this invention,
the inventive DPPs of the general formula I are used for the mass
coloration of polyvinyl chloride, polyamides and, especially,
polyolefins such as polyethylene and polypropylene as well as for
the preparation of paint systems, including powder coatings, inks,
printing inks, color filters and coating colors.
[0156] Illustrative examples of preferred binders for paint systems
are alkyd/melamine resin paints, acryvmelamine resin paints,
cellulose acetate/cellulose butyrate paints and two-pack system
lacquers based on acrylic resins which are crosslinkable with
polyisocyanate.
[0157] According to observations made to date, the inventive DPPs
of the general formula I can be added in any desired amount to the
material to be colored, depending on the end use requirements. In
the case of high molecular weight organic materials, for example,
the fluorescent DPP analogues of the general formula I prepared
according to this invention can be used in an amount in the range
from 0.01 to 50, preferably from 0.01 to 5% by weight, based on the
total weight of the colored high molecular weight organic
material.
[0158] Hence, another embodiment of the present invention relates
to a composition comprising
[0159] (a) 0.01 to 50, preferably 0.01 to 5, particularly preferred
0.01 to 2% by weight, based on the total weight of the colored high
molecular organic material, of a DPP of the general formula I
according to the present invention, and
[0160] (b) 99.99 to 50, preferably 99.99 to 95, particularly
preferred 99.99 to 98% by weight, based on the total weight of the
colored high molecular organic material, of a high molecular
organic material, and
[0161] (c) if desired, customary additives such as rheology
improvers, dispersants, fillers, paint auxiliaries, siccatives,
plasticizers, UV-stabilizers, and/or additional pigments or
corresponding precursors in effective amounts, such as e.g. from 0
to 50% by weight, based on the total weight of (a) and (b).
[0162] To obtain different shades, the inventive DPPs of the
general formula I may advantageously be used in admixture with
fillers, transparent and opaque white, colored and/or black
pigments as well as customary luster pigments in the desired
amount.
[0163] For the preparation of paint systems, coating materials,
color filters, inks and printing inks, the corresponding high
molecular weight organic materials, such as binders, synthetic
resin dispersions etc. and the inventive DPPs of the general
formula I are usually dispersed or dissolved together, if desired
together with customary additives such as dispersants, fillers,
paint auxiliaries, siccatives, plasticizers and/or additional
pigments or pigment precursors, in a common solvent or mixture of
solvents. This can be achieved by dispersing or dissolving the
individual components by themselves, or also several components
together, and only then bringing all components together, or by
adding everything together at once.
[0164] Hence, a further embodiment of the present invention relates
to a method of using the inventive DPPs of the general formula I
for the preparation of dispersions and the corresponding
dispersions, and paint systems, coating materials, color filters,
inks and printing inks comprising the inventive DPPs of the general
formula I.
[0165] A particularly preferred embodiment relates to the use of
the inventive fluorescent DPPs of the general formula I for the
preparation of fluorescent tracers for e.g. leak detection of
fluids such as lubricants, cooling systems etc., as well as to
fluorescent-tracers or lubricants comprising the inventive DPPs of
the general formula 1. Usually, such lubricant compositions, e.g.
for a refrigerant, comprise an oil selected from the group
consisting of naphthalenic oils, paraffinic oils, alkylated benzene
oils, polyalkyl silicate oils, polyglycols, esters, polyether
polyols, polyvinyl ethers, polycarbonates, fluorinated silicones,
perfluoroethers, aromatic compounds with fluoroalkyloxy or
fluoroalkylthio substituents. The amount of the inventive DPP of
the general formula I in the lubricant is chosen generally in an
amount of from 100 to 1000 ppm. If the inventive compound I is
water-soluble, it could be used as tracer in water as well.
[0166] A particular embodiment of this invention concerns ink jet
inks comprising the inventive DPPs of the general formula I.
[0167] For the coloring of high molecular weight organic material,
the inventive DPPs of the general formula 1, optionally in the form
of masterbatches, usually are mixed with the high molecular weight
organic materials using roll mills, mixing apparatus or grinding
apparatus. Generally, the pigmented material is subsequently
brought into the desired final form by conventional processes, such
as calandering, compression molding, extrusion, spreading, casting
or injection molding. In order to prepare non-rigid moldings or to
reduce their brittleness it is often desired to incorporate
so-called plasticizers into the high molecular weight organic
materials prior to forming. Examples of compounds which can be used
as such plasticizers are esters of phosphoric acid, phthalic acid
or sebacic acid. The plasticizers can be added before or after the
incorporation of the inventive DPP analogues of the general formula
I into the polymers. It is also possible, in order to achieve
different hues, to add fillers or other coloring constituents such
as white, color or black pigments in desired amounts to the high
molecular weight organic materials in addition to the inventive DPP
analogues of the general formula I.
[0168] For colouring lacquers, coating materials and printing inks
the high molecular weight organic materials and the inventive DPPs
of the general formula 1, alone or together with additives, such as
fillers, other pigments, siccatives or plasticizers, are generally
dissolved or dispersed in a common organic solvent or solvent
mixture. In this case it is possible to adopt a procedure whereby
the individual components are dispersed or dissolved individually
or else two or more are dispersed or dissolved together and only
then are all of the components combined.
[0169] The present invention additionally relates to inks
comprising a coloristically effective amount of the inventive DPP
of the general formula I.
[0170] Processes for producing inks especially for ink jet printing
are generally known and are described for example in U.S. Pat. No.
5,106,412.
[0171] When mixing a DPP of the general formula I with polymeric
dispersants it is preferred to use a water-dilutable organic
solvent.
[0172] The weight ratio of the pigment dispersion to the ink in
general is chosen in the range of from 0.001 to 75% by weight,
preferably from 0.01 to 50% by weight, based on the overall weight
of the ink.
[0173] The preparation and use of color filters or color-pigmented
high molecular weight organic materials are well-known in the art
and described e.g. in Displays 14/2, 1151 (1993), EP-A-784085, or
GB-A-2,310,072.
[0174] The color filters can be coated for example using inks,
especially printing inks, which can comprise the inventive DPPs of
the general formula I or can be prepared for example by mixing a
DPP of the general formula I with chemically, thermally or
photolytically structurable high molecular weight organic material
(so-called resist). The subsequent preparation can be carried out,
for example, in analogy to EP-A-654 711 by application to a
substrate, such as a LCD, subsequent photostructuring and
development.
[0175] The present invention relates, moreover, to toners
comprising a DPP of the general formula I or a high molecular
weight organic material coloured with a DPP of the general formula
I in a coloristically effective amount.
[0176] In a particular embodiment of the process of the invention,
toners, coating materials, inks or colored plastics are prepared by
processing masterbatches of toners, coating materials, inks or
colored plastics in roll mills, mixing apparatus or grinding
apparatus.
[0177] The present invention additionally relates to colorants,
colored plastics, polymeric ink particles, or non-Impact-printing
material comprising an inventive DPP of the general formula I or a
high molecular weight organic material coloured with a DPP of the
general formula I in a coloristically effective amount.
[0178] A coloristically effective amount of the pigment dispersion
according to this invention comprising an inventive DPP I denotes
in general from 0.0001 to 99.99% by weight, preferably from 0.001
to 50% by weight and, with particular preference, from 0.01 to 5%
by weight, based on the overall weight of the material pigmented
therewith.
[0179] Further, the inventive compounds I can be used for textile
application and for the dying of paper.
[0180] The following examples illustrate various embodiments of the
invention, but the scope of the invention is not limited
thereto.
EXAMPLES
Example 1
[0181] 43
[0182] Compound 5:
[0183] To pre-dried t-amyl alcohol (40 ml) was added sodium (1.50
g, 0.0652 mol) with stirring under nitrogen and the mixture heated
to reflux (105-110.degree. C.) until all the sodium dissolved. The
solution was cooled to 25.degree. C., then the lactam ester 9 (5.03
g, 0.0218 mol) and ethyl benzoate (3.27 g, 0.0218 mol) were added.
The mixture was then heated to reflux for 5.5 h during which time
an orange solution developed. The cooled mixture was added to an
ice-cooled mixture of methanol (10 ml) and water (50 ml), acidified
dropwise with concentrated hydrochloric acid (3 ml) then extracted
with tetrahydrofuran/diethyl ether, dried (Na.sub.2SO.sub.4) and
concentrated. Recrystallisation from aqueous ethanol yielded amber
coloured crystals.
[0184] Yield 2.38 g (33%), m.p. 156-157.degree. C. (Found: C, 71.5;
H, 5.2; N, 4.2; C.sub.20H.sub.17NO.sub.4 requires C, 71.6, H, 5.1;
N, 4.2%). 8H 0.67 (3H, t, J 7.2, OCH.sub.2CH.sub.3), 3.56 (2H, q,
OCH.sub.2CH.sub.3), 7.40-7.56 (6H, m-lp-Ar--H), 7.62-7.68 (4H, m,
o-Ar--H), 9.52 (1H, br. s, NH). m/z 335 (M.sup.+, 54%), 289 (100),
105 (56).
[0185] Compound 6:
[0186] A mixture of compound 5 (10 g, 0.0299 mol) and Dowtherm A
(200 ml) was heated to 230-240.degree. C. under nitrogen for 64 h.
The solution was then cooled to 250.degree. C. and added dropwise
to petrol ether 40-60 (300 ml) upon which a fluorescent orange
solid precipitated. This was filtered off, washed with further
hexane and dried in vacua. Yield 3.48 g (40%). (Found: C, 74.9; H
4.2; N 4.8%. C.sub.18H.sub.11NO.sub.3 requires C, 74.7; H, 3.8; N,
4.8). m/z289 (M.sup.+, 100%), 204 (20), 105 (35), 77 (35).
[0187] Compound 7:
[0188] To a suspension of sodium hydride (0.20 g, 55-65% dispersion
in mineral oil) in tetrahydroturan (100 ml) was added compound 6
under nitrogen at 25.degree. C. (1.0 g, 0.0034 mol) and the mixture
was heated briefly to reflux during 5 mins. The solution was cooled
to 25.degree. C., then benzyl bromide (0.70 g, 0.0041 mol) was
added. The solution was heated to reflux during 19 h, then cooled.
Water (50 ml) was added and the mixture extracted with a
tetrahydrofuran/ethyl acetate solvent mixture. The organic extracts
were concentrated and the residue mixed with petrol ether 40-60 and
treated in an ultrasonic bath for 20 mins. The product was filtered
off and dried in vacua. Yield 0.97 g (74%). (Found: C, 78.8; H,
4.9; N, 3.6%. C.sub.25H.sub.17NO.sub.3 requires C, 79.1; H, 4.5; N,
3.7). m/z379 (M+, 35%), 105 (50), 91(100), 77(20).
[0189] Compound 8:
[0190] A mixture of compound 7 (10 g, 0.0264 mol),
N,N'-dicyclohexylcarbod- iimide (13.5 g, 0.0655 mol),
dichloromethane (300 ml), trifluoroacetic acid (3 drops) and
aniline (5 g, 0.0538 mol) was stirred under nitrogen for 16 h at
40.degree. C. Further aniline (15 g, 0.1613 mol) and
N,N'-dicyclohexylcarbodiimide (10 g, 0.0485 mol) were added and
heating continued for 24 h. The mixture was then concentrated. The
residue was recrystallised from 1,4-dioxan then washed with hot
isopropyl alcohol, methanol and water then dried in vacuo.
Fluorescent orange solid, yield 1.87 g, (16%). (Found: C, 81.2; H,
5.3; N, 6.4%. C.sub.31H.sub.22N.sub.2O- .sub.2 requires C 81.9, H
4.9, N 6.2). m/z 454 (M.sup.+, 100%).
Example 2
[0191] 44
[0192] Compound 11:
[0193] To pre-dried t-amyl alcohol (230 ml) was added sodium (6.82
g, 0.2967 mol) with stirring under nitrogen and the mixture heated
to reflux (105-110.degree. C.) until all the sodium dissolved. The
solution was cooled to 70.degree. C. and then the lactam ester 10
(26.29 g, 0.0989 mol) and ethyl 4-chlorobenzoate (18.27 g, 0.0990
mol) were added. The mixture was then heated to reflux for 22 h
during which time an orange solution developed. The mixture was
then cooled and acidified with 10% hydrochloric acid (250 ml), then
extracted with tetrahydrofuran/ethyl acetate, the organic extracts
washed with water and then concentrated. The solid residue was
recrystallised from an ethanol/isopropylalcohol/wat- er mixed
solvent system to a yield beige coloured crystals which were
filtered off and dried in vacuo. Yield 31.36 g (78%). Found: C,
59.4; H, 4.1; N, 3.7, Cl, 17.4%. C.sub.20H.sub.15C.sub.12O.sub.4N
requires C, 59.4; H, 3.7; N, 3.5, Cl, 17.5).
[0194] Compound 12:
[0195] A mixture of compound 11 (15.0 g, 0.0371 mol) and Dowtherm A
(300 ml) was heated to 205-210.degree. C. during 48 h then cooled.
The mixture was then added dropwise to petrol ether 40-60 (1 l) and
the fluorescent purple was filtered off, washed with further petrol
and dried in vacuo. Yield 8.95 g (68%). (Found: C, 60.4; H, 2.8; N,
3.9%. Cs.sub.8HSCl.sub.2NO.sub.3 requires C 60.5, H 2.3, N 3.9).
m/z357 (M.sup.+, 100%), 139 (100), 111 (85), 75 (35).
Example 3
[0196] 45
[0197] Compound 13
[0198] To a mixture of intermediate 6 (0.99 g, 0.0034 mol) and
tetrahydrofuran (200 ml) under nitrogen at 25.degree. C. was added
sodium hydride (0.16 g, 55-65% mineral oil dispersion). The mixture
was heated briefly during 5 mins. to reflux, during which time gas
was evolved. The mixture was then cooled to 25.degree. C. and
methyl iodide (1.46 g, 0.0103 mol) was added. The solution was
stirred at 25.degree. C. during 16 h. Water (100 ml) was then added
and the mixture extracted with a tetrahydrofuran/ethyl acetate
mixed solvent. The combined organic extracts were then
concentrated, redissolved in DMSO (20 ml) and added dropwise to
water (200 ml). The fluorescent orange precipitate was filtered
off, washed with water and dried in vacuo. Yield 0.96 g (93%).
(Found C, 75.2; H, 4.5; N, 4.6%. C.sub.19H.sub.13NO.sub.3 requires
C, 75.2; H, 4.3; N, 4.6).
Example 4
[0199] Compound 14 46
[0200] A mixture of intermediate 6 (0.74 g, 0.0026 mol), di-t-butyl
dicarbonate (1.34 g, 0.0061 mol), 4-(N,N')-dimethylaminopyridine
(0.05 g, 0.0004 mol) and 0/.degree. tetrahydrofuran (100 ml) was
stirred at 25.degree. C. under nitrogen for 24 h. The reaction
mixture was concentrated, then the residue was mixed with methanol
(10 ml) and the solid precipitate was filtered off, washed with
methanol (5 ml) and dried in vacuo. Fluorescent yellow solid, yield
0.97 g (96%).
Example 5
[0201] 1.0 g of the DPP analogue 8 was mixed with 63.0 g of
polyvinyl chloride, 3.0 g of epoxidized soya oil, 2.0 g of
barium/cadmium thermal stabilizer and 32.0 g of dioctyl phthalate,
and the mixture was processed on a roller mill at 160.degree. C.
for 8 minutes to give a thin sheet. The PVC sheet thus produced is
characterized by its very strong fluorescent yellow-orange
color.
Example 6
[0202] In a 200 ml 4-neck flat bottom reactor equipped with a glass
stirrer, a thermometer, a nitrogen inlet tube, a bubble counter and
an addition funnel 60.0 g t-amylalcohol techn. and 5.24 g solid
sodium were poured. It was heated to 130.degree. C. ext.
temperature (int. temp. 110.degree. C.) and a small amount of
iron(III) trichloride was added. After the solid sodium has
completely disappeared, a mixture of 14.90 g p-chlorobenzonitrile,
14.27 g diisopropylsuccinimide and 42.70 g t-amylalcohol was added
within 2 hours. The temperature was decreased to 85.degree. C.
(int.) and the reaction mixture was stirred for 2 hrs. The
temperature is then decreased to 40.degree. C. and 0.32 g of
compound 6 described in example 1 were added. The reaction mixture
was then transferred within 15 min. in another reactor, poured into
a mixture of 275 ml demineralised water, 275 ml methanol and 120 ml
sulphuric acid at 40.degree. C. The pigment was conditioned during
18 hrs. After filtration and drying the obtained dark red pigment
powder was poured into 300 ml dimethylacetamide and further
conditioned for 5 hrs at 140.degree. C. 13.70 g (71%) of a bright
red pigment which in comparison to the pigment of comparative
example 1 exhibits a purer, brighter and yellower shade in mass
tone, along with a higher opacity. The gloss at 20.degree. C. was
slightly better than DPP Red BO. In white reduction, the pigment
showed equal colour strength. In white reduction 5:95, the weather
stability (2000 h WOM) was comparable to DPP Red BO.
[0203] Test Method:
[0204] 4.0 g untreated pigment were added to 46.0 g AM-paint
prepared as described below. The paint at 8% pigment conc. was
dispersed 1 hr. in Skandex with 200 g glass beads having a diameter
of 2 mm. The dispersed paint is drawn down (100 .mu.m) on a Mylar
sheet and poured on a glass plate. After 10 minutes, the Mylar
sheet and the glass plate were allowed to dry 30 minutes at
130.degree. C. in a hot air oven. The Mylar sheet had the following
colour properties (Datacolor 3890 calorimeter): lightness L*,
chroma C*, hue h and opacity (as .DELTA.Tr. over black). The
contrast paper was a clean and new standard Leneta. From the poured
out glass plates the gloss at 200 angle using a gloss meter ZGM
20.degree. from Zehntner Electronics Co. (Switzerland) was
determined.
[0205] A white reduction containing 5 parts of pigment and 95 parts
of white pigment was also prepared: 3.27 g of the previously
prepared mass tone paint were added to 26.73 g white AM-paint
(description below) and mixed with a simple glass stirrer to yield
30 g white reduction, which is drawn down on a Mylar sheet (100
.mu.m). From the Mylar sheet the colour strength was assessed.
[0206] Preparation of the AM-paint
1 Mass tone: 60.00 parts by weight Bayer Alkydal F 310, 60% in
solvent naphtol 16.00 parts by weight Cytec Cymel 327, 90% in
isobutanol 19.00 parts by weight xylol 2.00 parts by weight butanol
2.00 parts by weight 1-methoxy-2-propanol 1.00 parts by weight
silicone oil A, 1% in xylol White 20.00 parts by weight titanium
dioxide Kronos 2310 reduction: 47.67 parts by weight Bayer Alkydal
F 310, 60% in solvent naphtol 12.75 parts by weight Cytec Cymel
327, 90% in butanol 0.50 parts by weight Aerosil 200 1.59 parts by
weight 1-methoxy-2-propanol 1.59 parts by weight butanol 15.10
parts by weight xylol 0.80 parts by weight silicone oil A, 1% in
xylol
Comparative Example 1
[0207] Example 6 was repeated except that no compound 6 was added.
After filtration and drying in an oven under vacuum 16.03 g (83%)
bright red pigment exhibiting colour properties comparable to the
`state-of-the-art` (commercial DPP Red BO) were obtained. The
weather stability of this pigment is also comparable to the
`state-of-the-art` (2000 hrs WOM, white reduction 5:95).
* * * * *